JP4821152B2 - Process for producing cured conductive resin and composition for cured conductive resin - Google Patents

Description

  The present invention relates to a method for producing a cured conductive resin and a composition for a cured conductive resin, and more particularly relates to a method for producing a cured conductive resin containing a hydrophilic group-containing polymer compound.

  Since molded bodies such as optical elements constituting various display devices are formed of insulating plastic or glass, there is a problem in that they are easily charged and dust easily adheres to them. For example, an optical element made of plastic such as an antireflection sheet constituting a display device may adversely affect the image display function of the display device when charged and dust is deposited in a processing process or an assembly process of the display device. there were. As means for solving such a problem, a technique for preventing charging by forming a conductive film on the surface of a molded body (hereinafter also referred to as a base material) formed of plastic or glass has been proposed.

  As the conductive film, a metal film, a metal oxide film formed by an evaporation method or a sputtering method, or a metal oxide film formed by a sol-gel method is used. However, when a metal film or the like is formed by a vapor deposition method or a sputtering method, for example, when the base material is a plastic optical sheet or the like, it is cut into a necessary size from the viewpoint of reducing the manufacturing cost. Since it is necessary to form a metal film or the like on a large-area plastic sheet, a large-scale vapor deposition apparatus or sputtering apparatus is required, resulting in an increase in equipment costs. In addition, when a metal oxide film is formed by the sol-gel method, a heating step of about 200 ° C. is required, and therefore the base material and other layers other than the conductive film provided on the base material are heated. There was a problem of being damaged by.

  In order to solve the above problem, a conductive film made of a binder resin containing a conductive material has been considered. Since such a conductive film is formed by coating a resin composition for a conductive film, it can be easily formed even on a large area plastic sheet. No heating process that damages the like is required.

  As a conductive material constituting such a conductive film, a material that exhibits ion conductivity type conductivity by adsorbing water in the air has been proposed, and such ion conductivity type conductive material is proposed. As a surfactant, it is widely used. However, the surfactant has a low compatibility with the binder resin and is a low-molecular compound that easily moves in the film, so that it has a problem of bleeding out on the surface of the conductive film. When the surfactant bleeds out on the surface of the conductive film, the surface of the molded body that becomes the base material of the conductive film becomes cloudy white, the antistatic property of the conductive film is lost over time, The adhesion between the conductive film and the substrate or other layer adjacent to the conductive film may be reduced.

In order to solve this bleed-out problem, studies have been made on the use of hydrophilic group-containing polymer compounds having a plurality of hydrophilic groups as conductive materials. Examples of the hydrophilic group-containing polymer compound are those that exhibit an ionic conductivity type in which the hydrophilic group is expressed by adsorbing moisture in the air, or electrons that are expressed by doping the hydrophilic group into a π-conjugated compound. Some have conductivity type conductivity (see, for example, Patent Documents 1 and 2). Such a hydrophilic group-containing polymer compound is difficult to move in the film, and therefore is difficult to bleed out on the surface of the conductive film.
JP-A-9-78000 (Claim 1) JP 2001-270999 A (Claim 1)

  Since the hydrophilic group-containing polymer compound described above has a plurality of hydrophilic groups, it is easily dissolved or dispersed in water or a mixed solvent containing water. Therefore, when forming a conductive film containing a hydrophilic group-containing polymer compound, a resin using water or a mixed solvent containing a large amount of water as a solvent and a water-soluble or water-dispersible resin as a binder resin A composition was prepared. The hydrophilic group-containing polymer compound has the above hydrophilicity because it is difficult to dissolve or disperse in an organic solvent and has low compatibility with a resin having no hydrophilic group due to the action of the hydrophilic group of the compound. In forming a conductive film containing a group-containing polymer compound, a resin composition containing an organic solvent as a solvent and a resin composition containing no solvent (referred to as “solvent-free resin composition” in this specification) .) Is not used.

  However, when a resin composition using water or a mixed solvent containing a large amount of water as a solvent is used for forming the conductive film, the following adverse effects occur.

  First, the conductive film formed of the resin composition containing a large amount of water has a problem that moisture easily remains even after a solvent drying step. If moisture remains in the conductive film, the moisture easily oozes out to the surface of the conductive film, and the conductive film and the substrate or other layer provided adjacent to the conductive film are in close contact with each other. May deteriorate. In addition, when an element that dislikes water is used together with a member provided with such a conductive film in the manufacture of a display device, the performance of the element deteriorates due to moisture that has oozed out on the surface of the conductive film. Sometimes.

  In addition, in a resin composition that uses water or a mixed solvent containing a large amount of water as a solvent, it is necessary to select a water-soluble or water-dispersible resin having a hydrophilic group as the binder resin. There was a problem that the range of selection of was narrowed. In particular, recently, from the viewpoint of simplifying the production process, functional films such as hard coat layers that prevent the substrate from being scratched and plastic molded articles may be made conductive, but water or the like may be added. When forming a functional film or a molded body having conductivity with a resin composition as a solvent, it is difficult to select a binder resin suitable for the function of the functional film or the molded body. For example, since a hard coat layer is required to have high hardness and scratch resistance, an ionizing radiation curable resin may be used as a binder resin, but most commonly used ionizing radiation curable resins are water or It is difficult to dissolve or disperse in a mixed solvent containing a large amount of water. Therefore, when imparting conductivity to the hard coat layer using the above-described hydrophilic group-containing polymer compound, it is impossible to select such a commonly used ionizing radiation curable resin.

  The present invention has been made to solve the above-mentioned problems, and its first object is to include an element that improves adhesion with a substrate or layer provided adjacently and dislikes water. A method for producing a cured cured cured resin, in which the performance of the element is difficult to deteriorate even when used in a device, and the binder resin as a constituent material can be selected from various organic solvent-soluble or solvent-free resins Is to provide. The second purpose is to improve the adhesion with the substrate and layer provided adjacent to each other, and even if used in an apparatus containing an element that dislikes water, it is difficult to lower the performance of the element, and An object of the present invention is to provide a composition for a cured cured resin, which can form a cured cured resin in which a binder resin as a constituent material can be selected from various organic solvent-soluble or solventless resins. In this specification, “organic solvent-soluble resin” refers to a resin that dissolves or disperses in an organic solvent, and “solvent-free resin” refers to a resin composition that does not include a solvent (organic solvent and water). It shall refer to the resin constituting the product.

  The method for producing a cured conductive resin according to the first aspect of the present invention for solving the above-described problem has a plurality of hydrophilic groups and a lipophilic group bonded to at least a part of the plurality of hydrophilic groups. A preparation step for preparing a composition for a cured cured resin containing a hydrophilic group-containing polymer compound, at least one of an ionizing radiation curable resin and a thermosetting resin, and an organic solvent; A forming step of forming a coating film or a molded body with the composition for cured conductive resin, a drying step of drying the organic solvent contained in the coating film or the molded body, and the coating film or the molded body. And a curing step for curing (hereinafter, this production method is referred to as “production method I”).

  According to this invention, since the lipophilic group is bonded to the hydrophilic group of the hydrophilic group-containing polymer compound, the hydrophilic group-containing polymer compound is easily dissolved or uniformly dispersed in the organic solvent. The composition for cured conductive resin can be prepared with an organic solvent. Therefore, since the obtained conductive resin cured product is unlikely to contain moisture, it is difficult for the moisture to ooze out on the surface of the conductive resin cured product, and adhesion between the conductive resin cured product and the substrate or layer provided adjacent thereto Even if the device is used in an apparatus including an element that dislikes water, the performance of the element is hardly lowered. Moreover, according to this invention, since the organic solvent is used as the solvent, various resins that can be dissolved or dispersed in the organic solvent can be selected as the binder resin. Furthermore, according to the present invention, the lipophilic group bonded to the hydrophilic group can be dissociated by the drying process (heating process) and / or the curing process (ionizing radiation irradiation process or heating process). When the hydrophilic group of the functional group-containing polymer compound is exposed, the conductivity of the cured conductive resin is exhibited and the antistatic property is exhibited. In addition, when the lipophilic group is bonded to only part of the hydrophilic group of the hydrophilic group-containing polymer compound contained in the composition for cured conductive resin, the parent step is used in the drying step and the curing step. Even if the oily group is not dissociated, the obtained conductive resin cured product may develop conductivity.

  The method for producing a cured conductive resin according to the second embodiment of the present invention for solving the above-described problem has a plurality of hydrophilic groups and a lipophilic group bonded to at least a part of the plurality of hydrophilic groups. A preparation process for preparing a solventless conductive resin cured composition comprising a hydrophilic group-containing polymer compound and at least one of an ionizing radiation curable resin and a thermosetting resin; It includes a forming step of forming a coating film or a molded body with the composition for cured conductive resin, and a curing step of curing the coating film or the molded body.

  According to this invention, since the lipophilic group is bonded to the hydrophilic group of the hydrophilic group-containing polymer compound, the compatibility between the hydrophilic group-containing polymer compound and the binder resin is improved. A solvent-type composition for a cured conductive resin can be prepared. Therefore, since it is difficult for moisture to be contained in the obtained cured conductive resin, it is possible to prevent adverse effects caused by moisture contained in the cured conductive resin. Moreover, according to this invention, since a solventless type composition for conductive resin cured products can be prepared, various solventless resins can be selected as the binder resin. Furthermore, according to this invention, since the lipophilic group bonded to the hydrophilic group can be dissociated by the curing step, the conductive group is exposed by exposing the hydrophilic group of the hydrophilic group-containing polymer compound. The cured product exhibits electrical conductivity and exhibits antistatic properties. In addition, when the lipophilic group is bonded only to a part of the hydrophilic group of the hydrophilic group-containing polymer compound contained in the composition for cured conductive resin, the lipophilic group is not present in the curing step. Even if it does not dissociate, the obtained conductive resin cured product may exhibit conductivity.

  The method for producing a cured conductive resin according to the present invention is the method for producing a cured cured resin according to the first aspect, wherein the hydrophilic group-containing material is contained in at least one of the drying step and the curing step. It is preferable to dissociate at least part of the lipophilic group of the polymer compound from the hydrophilic group.

  According to this invention, at least part of the lipophilic group is dissociated from the hydrophilic group by irradiation with ionizing radiation or heating in the drying process or the curing process, so that the conductivity of the obtained conductive resin cured product is improved. To do.

  The method for producing a cured cured resin according to the present invention is the method for producing a cured cured resin according to the second aspect, wherein the hydrophilic group-containing polymer compound has a lipophilic group in the curing step. It is preferable to dissociate at least a part from the hydrophilic group.

  The method for producing a cured cured resin according to the present invention is the method for producing a cured cured resin, wherein at least a part of the lipophilic group of the hydrophilic group-containing polymer compound is added after the curing step. It is preferable to further include a dissociation step for dissociating from the hydrophilic group.

  According to this invention, since the dissociation process which dissociates a lipophilic group from a hydrophilic group is included after the said hardening process, the electroconductivity of the obtained conductive resin hardened | cured material can be improved.

  In the method for producing a cured conductive resin according to the present invention, in the above-described method for producing a cured cured resin, it is preferable that the composition for a cured cured resin further includes a π-conjugated polymer compound.

  According to this invention, since the composition for a cured conductive resin further includes a π-conjugated polymer compound, in the obtained conductive resin cured product, the hydrophilic group-containing polymer compound having a hydrophilic group is π-conjugated. It functions as a dopant with respect to the polymer compound. Therefore, since the obtained conductive resin cured product exhibits electron conductivity type conductivity, it is stable and has high conductivity without depending on humidity. As a result, it is possible to obtain a cured conductive resin that is used not only for antistatic purposes but also for electromagnetic wave shielding, for example.

  In the method for producing a cured conductive resin according to the present invention, in the method for producing a cured conductive resin, the π-conjugated polymer compound is preferably polythiophene or a derivative thereof, and further, the hydrophilic group is It is preferably at least one selected from the group consisting of a sulfone group, a carboxyl group and a phosphate group.

  In the method for producing a cured conductive resin of the present invention, in the above-described method for producing a cured cured resin, it is preferable that the composition for a cured cured resin further includes a filler.

  A composition for cured conductive resin according to the first embodiment of the present invention for solving the above-described problem is a hydrophilic group-containing polymer compound having a plurality of hydrophilic groups, an ionizing radiation curable resin, and thermosetting. It includes at least one resin of a hydrophilic resin and an organic solvent, and a lipophilic group is bonded to at least a part of the plurality of hydrophilic groups.

  A composition for a cured conductive resin according to a second embodiment of the present invention for solving the above problems includes a hydrophilic group-containing polymer compound having a plurality of hydrophilic groups, an ionizing radiation curable resin, and thermosetting. Solvent-free composition for cured cured resin, comprising at least one of the hydrophilic resins, wherein a lipophilic group is bonded to at least a part of the plurality of hydrophilic groups. .

  The composition for cured conductive resin of the present invention preferably further includes a π-conjugated polymer compound in the composition for cured cured resin.

  According to the method for producing a cured conductive resin according to the first aspect of the present invention, the composition for cured conductive resin is prepared using an organic solvent instead of water as a solvent. It is hard for moisture to be contained in things. As a result, the obtained cured cured resin is preferably used even in an apparatus including an element that dislikes water because the adhesion with a substrate or layer provided adjacently is improved. Moreover, according to the manufacturing method of the cured conductive resin according to the first embodiment of the present invention, the composition for cured conductive resin is prepared using an organic solvent, so that it is dissolved or dispersed in an organic solvent as a binder resin. Various resins can be selected. Furthermore, according to the method for producing a cured conductive resin according to the first embodiment of the present invention, the lipophilic group bonded to the hydrophilic group can be dissociated by the drying step and / or the curing step. By exposing the hydrophilic group of the hydrophilic group-containing polymer compound, the conductivity of the cured conductive resin is manifested.

  According to the method for producing a cured conductive resin according to the second aspect of the present invention, since the solvent-free composition for cured cured resin is prepared, moisture is contained in the obtained cured cured resin. hard. As a result, it is possible to prevent harmful effects caused by moisture contained in the cured conductive resin. In addition, according to the method for producing a cured conductive resin according to the second embodiment of the present invention, a solvent-free composition for a cured cured conductive resin is prepared. Can be selected. Furthermore, according to the method for producing a cured conductive resin according to the second embodiment of the present invention, since the lipophilic group bonded to the hydrophilic group can be dissociated by the curing step, the hydrophilic group-containing high content can be obtained. By exposing the hydrophilic group of the molecular compound, the conductivity of the cured conductive resin is manifested.

  According to the composition for a cured conductive resin according to the first or second embodiment of the present invention, since the lipophilic group is bonded to the hydrophilic group of the hydrophilic group-containing polymer compound, water is used as a solvent. Even if not used, the hydrophilic group-containing polymer compound is dissolved, dispersed or compatible. Therefore, since it is difficult for moisture to be contained in the conductive resin cured product obtained by the composition for cured conductive resin, it is possible to prevent harmful effects caused by remaining moisture in the cured conductive resin. Moreover, according to the composition for conductive resin cured products according to the first or second embodiment of the present invention, various organic solvent-soluble or solvent-free resins can be selected as the binder resin.

  Hereinafter, the composition for a cured conductive resin, the cured conductive resin, and a method for producing the same according to the present invention will be described.

[Method for producing cured conductive resin]
(1) Method for producing a cured cured resin according to the first embodiment:
The manufacturing method of the cured conductive resin according to the first aspect of the present invention includes a preparation step for preparing the composition for cured conductive resin according to the first aspect of the present invention, and a composition for cured conductive resin. It includes a forming step for forming a coating film or a molded body of a product, a drying step for drying an organic solvent contained in the coating film or the molded body, and a curing step for curing the coating film or the molded body. The method for producing a cured conductive resin according to the first embodiment of the present invention may further include a dissociation step after the curing step. Here, the cured conductive resin formed as a coating film is referred to as “conductive resin cured film”, and the cured conductive resin formed as a molded body is referred to as “conductive resin cured molded body”.

(Preparation process)
The preparation step in the method for producing a cured conductive resin according to the first aspect of the present invention is a step of preparing the composition for cured conductive resin according to the first aspect of the present invention, that is, a plurality of hydrophilic properties. A hydrophilic group-containing polymer compound having a group, at least one of an ionizing radiation curable resin and a thermosetting resin (hereinafter sometimes referred to as a binder resin), and an organic solvent, and a plurality of hydrophilic groups It is a step of preparing a composition for a cured conductive resin in which a lipophilic group is bonded to at least a part of the functional group.

  Since the hydrophilic group-containing polymer compound contained in the composition for cured conductive resin of the present invention has a lipophilic group bonded to a hydrophilic group, it is easily dissolved or dispersed in an organic solvent. Therefore, since an organic solvent can be used as a solvent for the composition for a cured conductive resin, it is difficult for moisture to be contained in the obtained cured cured resin. As a result, since moisture hardly oozes out on the surface of the cured conductive resin, the adhesion between the cured conductive resin and the substrate or layer provided adjacent thereto is improved. In addition, since it is difficult for moisture to ooze out on the surface of the conductive cured product, the performance of the element is unlikely to deteriorate even when used in an apparatus including an element that dislikes water.

  The hydrophilic group-containing polymer compound is contained in order to develop the conductivity of the conductive resin cured product. Examples of the conductivity exhibited by the cured cured resin include ion conduction type and electron conduction type conductivity. The ion conductivity type conductivity is manifested by adsorption of moisture in the air to the hydrophilic group of the hydrophilic group-containing polymer compound and movement of ions in the moisture. Electron conductivity type conductivity is manifested when a hydrophilic group functions as a dopant for a π-conjugated bond compound having electron conductivity. In the present invention, the hydrophilic group-containing polymer compound itself is the main chain. This occurs when the resin has a π-conjugated bond, or when the composition for a cured conductive resin further contains a π-conjugated polymer compound. Hereinafter, the conductivity of the electron conduction type expressed by the hydrophilic group-containing polymer compound having a π-conjugated bond in the main chain may be referred to as “self-doped electron conduction type conductivity”. The electron conductivity type conductivity is higher than the ion conductivity type conductivity and is not affected by the humidity of the air.

  Examples of the hydrophilic group possessed by the hydrophilic group-containing polymer compound include an anionic group such as a sulfone group, a carboxyl group, and a phosphate group, or a cationic group such as a primary to quaternary amino group and an amide group. Can be mentioned.

  Examples of hydrophilic group-containing polymer compounds having an anionic group include monomers having a sulfonic acid group such as styrene sulfonic acid, monomers having a carboxyl group such as (meth) acrylic acid, 2-hydroxyethyl phosphate (meta ) A polymer or copolymer having a repeating unit of a monomer selected from the group of monomers having a phosphate group such as acrylate. Examples of the hydrophilic group-containing polymer compound having a cationic group include a monomer selected from the group of monomers having amino groups such as vinylamine and acrylamine, and monomers having amide groups such as acrylamide as repeating units. And a polymer or copolymer.

  The hydrophilic group-containing polymer compound preferably has a π-conjugated bond in the main chain. In such a hydrophilic group-containing polymer compound, since the hydrophilic group of the compound functions as a dopant for the π-conjugated bond, the obtained conductive resin cured product is a self-doped electron conduction type as described above. Conductivity. Therefore, when the hydrophilic group-containing polymer compound has a π-conjugated bond in the main chain, a cured conductive resin that exhibits high conductivity independent of humidity can be obtained. Accordingly, such a cured conductive resin is particularly useful when a higher level of conductivity than antistatic properties is required (for example, when electromagnetic shielding properties are required). In addition, the hydrophilic group which does not function as a dopant among the hydrophilic groups which such a hydrophilic group containing high molecular compound has contributes to electroconductivity of ion conduction type.

  A hydrophilic group-containing polymer compound having a π-conjugated bond in the main chain can be obtained by introducing a hydrophilic group into a polymer compound having a π-conjugated bond in the main chain. It can be obtained by using a π-conjugated monomer having a hydrophilic group. Examples of the polymer compound having a π-conjugated bond in the main chain include a hole transport polymer compound and an electron transport polymer compound. Examples of the hole transport polymer compound include a high molecular weight monomer such as pyrazoline, arylamine, stilbene, and triphenyldiamine, or a derivative of the high molecular weight. Examples of the electron transport polymer compound include polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyparaphenylene vinylene, polythiophene vinylene, poly (3,4-ethylenedioxythiophene), polythieno (3,4-thiophene), In addition to polydithieno (3,4,3 ', 4'-thiophene), polyfluorene, polyaniline, polyacene and / or derivatives thereof, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthra Examples include high molecular weight monomers of monomers such as dinomethane, fluorenone, diphenyldicyanoethylene, diphenoquinone, and 8-hydroxyquinoline, derivatives of these high molecular weight materials, and metal complexes of these high molecular weight materials.

  The polymerization ratio of the monomer having a hydrophilic group in the hydrophilic group-containing polymer compound is preferably 10 mol% or more. When the polymerization ratio of the monomer having a hydrophilic group is less than 10 mol%, the conductivity of the cured conductive resin is lowered and the antistatic property cannot be obtained. In addition, all the monomers which comprise a hydrophilic group containing high molecular compound may have a hydrophilic group.

  The upper limit of the weight average molecular weight of the hydrophilic group-containing polymer compound varies depending on the structure of the hydrophilic group-containing polymer compound from the viewpoint of solubility or dispersibility in an organic solvent. For example, the upper limit of the weight average molecular weight of a hydrophilic group-containing polymer compound having no π-conjugated bond in the main chain is about 1 million. Further, the upper limit of the weight average molecular weight of the hydrophilic group-containing polymer compound having a π-conjugated bond in the main chain is about 500,000. When the weight average molecular weight of each hydrophilic group-containing polymer exceeds the above upper limit, it becomes difficult to dissolve or disperse in an organic solvent even if a lipophilic group is bonded to the hydrophilic group.

  The lower limit of the weight average molecular weight of the hydrophilic group-containing polymer compound is about 3,000. When the weight average molecular weight of the hydrophilic group-containing polymer compound is less than 3,000, the molecular weight of the hydrophilic group-containing polymer compound is too low, and the strength of the cured conductive resin becomes weak. Here, the weight average molecular weight in this specification is a polyethylene glycol equivalent value measured using gel permeation chromatographic analysis (GPC).

  In the present invention, a lipophilic group is bonded to the hydrophilic group of the hydrophilic group-containing polymer compound. As a result, the hydrophilic group-containing polymer compound is easily dissolved or dispersed in an organic solvent, and an organic solvent can be used as a solvent for the composition for a cured conductive resin. A cured product can be obtained. Moreover, since the lipophilic group couple | bonded with the hydrophilic group can be dissociated by a subsequent hardening process etc., a hydrophilic group can be exposed and a conductive resin hardened | cured material with high electroconductivity can be obtained.

  Examples of the lipophilic group bonded to the hydrophilic group include an alkyl group having 1 to 20 carbon atoms. This alkyl group may be linear, branched or cyclic. When the carbon number of the alkyl group exceeds 20, the hydrophilic group-containing compound is difficult to dissolve or disperse in the organic solvent. Moreover, as another lipophilic group, the alkyl group which the functional group reactive with the sclerosing | hardenable group of a binder resin component can be mentioned. Since the hydrophilic group-containing polymer compound to which such a lipophilic group is bonded crosslinks with the binder resin component, the strength of the obtained conductive resin cured product is improved. However, since such a lipophilic group does not dissociate from the hydrophilic group when it crosslinks with the curable group of the binder resin component, it is hydrophilic to the extent that the conductivity required for the obtained cured conductive resin can be ensured. It is preferable that it is couple | bonded with the sex group.

  The lipophilic group does not need to be bonded to all the hydrophilic groups of the hydrophilic group-containing polymer compound, and the hydrophilic group-containing polymer compound is an organic material used in the composition for a cured conductive resin. What is necessary is just to couple | bond together to such an extent that it melt | dissolves or disperses in a solvent. The specific binding amount of the lipophilic group is appropriately determined according to the organic solvent used. In addition, when the lipophilic group is bonded to only a part of the hydrophilic group possessed by the hydrophilic group-containing polymer compound, the conductivity obtained even if the lipophilic group does not dissociate in the drying step and the curing step. The cured resin may exhibit conductivity.

  Examples of the method for binding a lipophilic group to a hydrophilic group include methods for esterifying, etherifying, acetylating, tosylating, tritylating, alkylsilylating, alkylcarbonylating, etc. The method of making or etherifying is preferred. Since the bond between the hydrophilic group and the lipophilic group by esterification or etherification is via oxygen, the bond energy is weak, and the lipophilic group is easily dissociated from the hydrophilic group by a subsequent dissociation step or the like. In order to bond a lipophilic group to a hydrophilic group by esterification, for example, the hydrophilic group of the hydrophilic group-containing polymer compound is chlorinated with a chlorinating agent such as phosphorus pentachloride or thionyl chloride, and then methanol or ethanol Esterification with an alcohol such as

  The lower limit of the blending ratio of the hydrophilic group-containing polymer compound in the composition for cured conductive resin varies depending on the type of conductivity to which the hydrophilic group-containing polymer compound contributes. For example, the lower limit of the blending ratio of the hydrophilic group-containing polymer compound that contributes to ion conductivity type conductivity is preferably about 3 parts by weight with respect to 100 parts by weight of the binder resin component. Moreover, it is preferable that the minimum of the mixture ratio of the hydrophilic group containing high molecular compound which contributes to electroconductivity of self-doping electron conduction type is about 3 weight part with respect to 100 weight part of binder resin components. When the blending ratio of the hydrophilic group-containing polymer compound is less than the above lower limit, the conductivity of the obtained conductive resin cured product is lowered and the antistatic property is lowered. Here, particularly when the blending ratio of the hydrophilic group-containing polymer compound contributing to the conductivity of the self-doped electron conduction type is 10 parts by weight or more, the level is higher than the antistatic property (for example, electromagnetic wave shielding property). A cured conductive resin that exhibits electrical conductivity can be obtained.

  The upper limit of the blending ratio of the hydrophilic group-containing polymer compound is preferably about 90 parts by weight. When the blending ratio of the hydrophilic group-containing polymer compound exceeds 90 parts by weight, the strength of the obtained conductive resin cured product is extremely lowered. In addition, the mixture ratio of the hydrophilic group containing high molecular compound which functions as a dopant when the (pi) conjugated polymer compound is further contained in the composition for cured conductive resins will be described later.

  The ionizing radiation curable resin or thermosetting resin is contained in the composition for cured conductive resin as a binder resin. These resins may be used alone or as a mixture. Resin used as binder resin is suitably selected according to the use of the conductive resin hardened material obtained. For example, when the obtained conductive resin cured product is used as an optical sheet that requires transparency or a coating film thereof, a resin whose total light transmittance of the conductive resin cured product is 85% or more is used. Selected as a binder resin.

  Since the organic solvent is used as the solvent in the composition for cured conductive resin according to the first embodiment of the present invention, various resins that can be dissolved or dispersed in the organic solvent can be selected as the binder resin. The resin that can be selected as the binder resin includes so-called organic-inorganic hybrid polymers in which a metal such as silicon is contained in the main chain.

  The ionizing radiation curable resin is a resin having a functional group (hereinafter referred to as an ionizing radiation curable group) that undergoes a polymerization reaction such as photo radical polymerization, photo cation polymerization, or photo anion polymerization or a crosslinking reaction upon irradiation with ionizing radiation. In the composition for cured conductive resin, it is contained as a monomer or oligomer having an ionizing radiation curable group. Here, “ionizing radiation” refers to ultraviolet rays, visible rays, electron beams, β rays, X rays, γ rays, α rays, etc. having energy quanta capable of polymerizing or crosslinking molecules. Used.

  Preferred examples of the ionizing radiation curable group include an ethylenically unsaturated bond such as an acrylic group and a vinyl group, or a cyclic ether bond such as an epoxy group, a vinyl ether group, and an oxetanyl group. Monomers and oligomers having such ionizing radiation curable groups readily undergo photoradical polymerization or photocationic polymerization upon irradiation with ionizing radiation.

  Examples of the oligomer having an ethylenically unsaturated bond include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Can do. In addition, (meth) acrylate means a methacrylate or an acrylate.

  Monofunctional monomers having an ethylenically unsaturated bond include vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactone, vinylimidazole, vinylpyridine or styrene, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl. (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl acrylate, paracumylphenoxyethyl (meth) acrylate , Nonylphenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoborni Examples include (meth) acrylic monomers such as (meth) acrylate, cyclohexyl (meth) acrylate, benzyl methacrylate, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylate, and acryloylmorpholine. it can.

  Examples of polyfunctional monomers having an ethylenically unsaturated bond include ethylene glycol di (meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (Meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, and the like.

  Examples of the oligomer having a cyclic ether bond include epoxy oligomers such as bisphenol type epoxy resins and novolak type epoxy compounds, vinyl ether type oligomers such as fatty acid type vinyl ethers and aromatic vinyl ethers.

  Examples of the monomer having a cyclic ether bond include ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, 1,2,8,9-diepoxy limonene, 3,4-epoxycyclohexyl methyl, 3 ′, 4 ′. -Epoxy monomers such as epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate, or oxetane monomers represented by the following chemical formulas 1 to 3 can be exemplified.

(Wherein R1 represents hydrogen, fluorine, alkyl group, fluoroalkyl group, allyl group, aryl group or furyl group, m represents an integer of 1 to 4, Z represents oxygen or sulfur, and R2 represents m Depending on the value, it represents a 1 to 4 valent organic group, n represents an integer of 1 to 5, p represents an integer of 0 to 2, R3 represents hydrogen or an inert monovalent organic group, R4 Represents a hydrolyzable functional group.)

  In the oxetane monomers represented by the above chemical formulas 1 to 3, the alkyl group or fluoroalkyl group to be R1 usually has about 1 to 6 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, and a prokyl group. Group, butyl group and the like. In the oxetane monomers represented by the above chemical formulas 1 to 3, the aryl group to be R1 is usually a phenyl group or a naphthyl group, and these aryl groups may be substituted with a substituent such as an alkyl group. In the oxetane-based monomer represented by the above chemical formula 1, the organic group represented by R2 includes, for example, an alkyl group or a phenyl group when m is 1, and a carbon when m is 2 or 3. Examples include a linear or branched alkylene group of 1 to 12 or a linear or branched polyalkyleneoxy group. When m is 4, a methyl group or when m is 2 or 3 The polyfunctional group similar to the applied organic group is mentioned.

  Examples of the polymer having a cyclic ether bond include an epoxy macromonomer having an epoxy-containing group represented by the following formula 3 at the terminal described in JP-A-7-247313 and JP-A-7-309856. In addition, oxetane-based macromonomers having an oxetane-containing group represented by the following formula 4 at the terminal, and various epoxy resins such as SANBO AR-G (trade name: Sanpo Chemical Laboratory Co., Ltd.) and E-154 as commercial products (trade names: Japan Epoxy Co., Ltd.) and Epofriend (trade name: Daicel Chemical Industries, Ltd.).

(However, in Formulas 4 and 5, A is one type of substituent selected from a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 6 carbon atoms. P is 0 or 1. When p is 0. , Q represents an integer of 1 to 8, and r is 0 or 1. When p is 1, q represents an integer of 1 to 5, and r represents an integer of 1 to 4. -C _p H _2q -Represents a linear alkylene group or a branched alkylene group.

  When ultraviolet rays are used as the ionizing radiation, a photopolymerization initiator is added to the composition for a cured conductive resin.

  As the photopolymerization initiator when the ionizing radiation curable group is an ethylenically unsaturated bond, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldiones Compounds, disulfide compounds, thiuram compounds, fluoroamine compounds and the like are used. Specific examples of such photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyl Dimethyl ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, benzophenone, etc., among which 1-hydroxy-cyclohexyl-phenyl-ketone or 2-methyl-1 [4- (methylthio) phenyl]- A preferred example is 2-morpholinopropan-1-one. In particular, 1-hydroxy-cyclohexyl-phenyl-ketone or 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one starts a polymerization reaction by irradiation with ultraviolet rays even in a small amount. It is preferable because it is promoted. These photopolymerization initiators may be used alone or in combination of two or more. Preferable examples of commercially available photo radical polymerization initiators include Irgacure 184 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd., which is 1-hydroxy-cyclohexyl-phenyl-ketone. In addition, the addition amount of a photoinitiator is 3-15 weight part normally with respect to 100 weight part of ionizing radiation curable resin components.

Examples of the photopolymerization initiator when the ionizing radiation curable group is a cyclic ether bond include a diazonium salt represented by the chemical formula ArN ²⁺ Z ⁻ , a sulfonium salt represented by the chemical formula R ₃ S ⁺ Z ⁻ , and a chemical formula R ₂ I ⁺ Z ^- onium salts such as iodonium salts represented by is preferably used. In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and Z ⁻ represents a non-basic and non-nucleophilic anion. In the onium salt, the aryl group represented by Ar or R is usually a phenyl group or a naphthyl group, and these aryl groups may be substituted with a substituent such as an alkyl group. Further, when there are a plurality of R in the molecule, they may be the same or different. In the onium salt, the anion represented by Z ⁻ includes tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), hexafluoro Phosphate ion (PF ₆ ⁻ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), peroxy Examples include chlorate ions (ClO ₄ ⁻ ). A preferred commercially available diazonium salt is Syracure UVI-6990 (trade name) manufactured by Dow Chemical Japan Co., Ltd., and a preferred sulfonium salt commercially available is Adekaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd. (Trade name) and Adeka optomer SP-170 (trade name) are listed, and examples of a commercially available iodonium salt include RHODROSIL PHOTOINITITOR 2074 (trade name) manufactured by Rhodia Japan. In addition, the addition amount of this photoinitiator is 0.1-20 weight part normally with respect to 100 weight part of ionizing radiation curable resin components.

  A thermosetting resin is a resin having a functional group (hereinafter referred to as a thermosetting group) that undergoes a polymerization reaction or a cross-linking reaction with the same or other types of functional groups by heating. The composition contains monomers and oligomers.

  As a thermosetting resin monomer or oligomer, alkoxy group, hydroxyl group, carboxyl group, amino group, epoxy group, isocyanate group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, vinyl group, cyano group, Examples thereof include monomers or oligomers having a thermosetting group such as a methylol group or an active methylene group. In addition, the thermosetting group has a blocking agent bonded to a reactive functional group such as a block isocyanate group, and when heated, the decomposition reaction of the blocking agent proceeds to increase the polymerizability and crosslinkability. The functional group shown may be sufficient. In addition, as a thermosetting resin monomer, an organometallic compound such as an organosilicon compound (silicon alkoxide or silane coupling agent), an organotitanium compound (titanate coupling agent), or an organoaluminum compound that is usually used as a coupling agent. Can also be used.

  Examples of organosilicon compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltriacetoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxypropyltrieth Sisilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, 3-acryloyloxypropyltrimethoxy Silane, 3-acryloyloxypropyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, can be cited 3-cyanoethyl triethoxysilane. Examples of the organosilicon compound in which two alkyl groups are substituted include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and 3-glycidyl. Oxypropylmethyldimethoxysilane, 3-glycidyloxypropylphenyldiethoxysilane, 3-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3 -Methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyl methyl diethoxy silane, 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane. Among these organosilicon compounds, an organosilicon compound having a reactive group is easily cured and strongly bonded to other monomers and oligomers, so that the strength of the obtained conductive resin cured product is improved. Preferred examples of commercially available organosilicon compounds include Composeran (trade name) and Juliano (trade name) manufactured by Arakawa Chemical Industries, Ltd.

  Examples of the organic titanium compound include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Can do. Preferred organic titanium compounds that are commercially available include Anomoto Co., Ltd. Preneact KR-TTS, KR-46B, KR-55, KR-41B, KR-38S, KR-138S, KR-238S, 338X, KR-44. , KR-9SA, KR-ET (trade names) and the like.

  The monomers and oligomers having the thermosetting groups exemplified above are combined in the reactive ones and contained in the composition for cured conductive resin. Examples of thermosetting resins obtained by combining such monomers and oligomers include phenol resins, epoxy resins, urea resins, melamine resins, and organic-inorganic hybrid polymers.

  The composition for cured conductive resin of the present invention preferably further contains a π-conjugated polymer compound.

  The π-conjugated polymer compound is a polymer compound that exhibits electron conductivity type conductivity having a π-conjugated structure in the main chain, and exhibits high conductivity when doped with electrons or holes. When such a π-conjugated polymer compound is contained in the composition for cured conductive resin, the hydrophilic group of the hydrophilic group-containing polymer compound serves as a dopant for the π-conjugated polymer compound. Since it functions, the electroconductivity of the obtained conductive resin cured | curing material can be improved. Therefore, the cured conductive resin thus obtained is particularly useful when a level of conductivity higher than the antistatic property is required (for example, when electromagnetic shielding properties are required). Hereinafter, the π-conjugated polymer compound and the hydrophilic group-containing polymer compound doped into the π-conjugated polymer compound are referred to as “electron conductive material”.

  Examples of the π-conjugated polymer compound include compounds such as polythiophene, polyacetylene, polypyrrole, polyparaphenylene, polyfluorene, polyaniline, and polyacene, and derivatives of these compounds. Among them, polythiophene or a derivative thereof is preferably used. . Since polythiophene and its derivatives have higher binding energy than other π-conjugated polymer compounds, there is an advantage that they are difficult to be decomposed by heating in the drying process or curing process, irradiation with ionizing radiation, and the like. Examples of the polythiophene derivative include polythiophene vinylene, poly (3,4-ethylenedioxythiophene), polythieno (3,4-thiophene), polydithieno (3,4,3 ', 4'-thiophene) and the like. When polythiophene is used as the π-conjugated polymer compound, the hydrophilic group of the hydrophilic group-containing polymer compound is preferably an anionic group such as a sulfone group, a carboxyl group, or a phosphate group. A preferable combination of the π-conjugated polymer compound and the hydrophilic group-containing polymer compound constituting the electron conductive material includes a combination of polythiophene and polystyrene sulfonic acid.

  The π-conjugated polymer compound preferably has a weight average molecular weight of 500 to 1,000,000. When the weight average molecular weight exceeds 1,000,000, it becomes difficult for the π-conjugated polymer compound to be dissolved or dispersed in the organic solvent. Moreover, when a weight average molecular weight is less than 500, the intensity | strength of the obtained conductive resin hardened | cured material will fall.

  The blending ratio of the hydrophilic group-containing polymer compound to the π-conjugated polymer compound in the electron conductive material is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the π-conjugated polymer compound. More preferably, it is -100 weight part. When the blending ratio of the hydrophilic group-containing polymer compound exceeds 150 parts by weight, there is a problem that ion conductivity that is weak against changes in humidity becomes dominant. In addition, when the blending ratio of the hydrophilic group-containing polymer compound is less than 1 part by weight, there is a problem that the hydrophilic group-containing polymer compound does not sufficiently function as a dopant and desired conductivity cannot be obtained. is there.

  The blending ratio of the electron conductive material is preferably 1 part by weight or more with respect to 100 parts by weight of the binder resin component when the obtained conductive resin cured product is used for antistatic use. More preferably. Moreover, when using the obtained conductive resin hardened | cured material for the use of an electromagnetic wave shield, it is preferable that it is 5 weight part or more with respect to 100 weight part of binder resin components, and it is still more preferable that it is 15 weight part or more. In addition, the upper limit of the blending ratio of the electron conductive material is usually about 200 parts by weight, preferably about 150 parts by weight, more preferably about 100 parts by weight with respect to 100 parts by weight of the binder resin component. preferable. When the blending ratio of the electron conductive material exceeds 200 parts by weight, the strength of the obtained conductive resin cured product is extremely lowered.

  The composition for cured conductive resin according to the first embodiment of the present invention can contain various organic solvents as a solvent.

  In the present invention, since water or a mixed solvent containing a large amount of water is not used as a solvent, there is an effect that no adverse effect due to the water contained in the obtained conductive resin cured product occurs. In particular, when a conductive resin cured film is formed using this composition for a cured conductive resin, an organic solvent that swells the base material and other layers as the base of the conductive resin cured film is used as a solvent. As a result, the adhesion between the cured conductive resin film and the base material or other layer serving as the base can be improved. On the other hand, in the conventional resin composition for conductive films, water or a mixed solvent containing water is used as a solvent. The effect was not obtained.

  Examples of the organic solvent include alcohols such as isopropyl alcohol, methanol, and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene, and the like Aromatic hydrocarbons; or a mixed solvent thereof can be used. The organic solvent may contain a small amount of water as long as it does not affect the adhesion between the cured conductive resin and the substrate or the performance of the apparatus in which the cured conductive resin is used. For example, when the content of water contained in the organic solvent is 3% by weight or less, the above adhesion does not decrease. However, when a cured conductive resin is used in a device (for example, an organic electroluminescence device) whose performance deteriorates even with a small amount of moisture, the composition for the cured cured resin with an organic solvent that does not contain water at all. It is preferable to adjust things.

  The boiling point of the organic solvent is preferably 120 ° C. or lower. When the boiling point of the organic solvent exceeds 120 ° C., it becomes difficult to handle the composition for a cured conductive resin, and particularly in the drying step when a coating film is formed with the composition for a cured cured resin. May adversely affect the substrate.

  Further, the blending ratio of the organic solvent can uniformly dissolve or disperse the solid content, and the solid content does not aggregate when the composition for a cured cured resin is prepared. The viscosity of the composition for cured resin is appropriately determined so as to be easily formed into a coating film or a molded body in the forming step. The specific blending ratio of the organic solvent is usually 50 to 95.5 parts by weight, preferably 70 to 90 parts by weight when the total amount of the organic solvent and the solid content is 100 parts by weight. Here, the solid content includes a hydrophilic group-containing polymer compound, a binder resin component and various additives, and when the π-conjugated polymer compound is contained in the composition for cured conductive resin Further, a π-conjugated polymer compound is included.

  The so-called “hard coat layer” (JIS 5600-5-4: 1999) is used to improve the performance such as scratch resistance and strength of the cured conductive resin of the present invention. When it is used as a binder component, it is preferable that the binder component is formed using the ionizing radiation curable resin composition mentioned above. The film thickness upon curing as the hard coat layer is preferably in the range of 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is in this range, the function as the hard coat layer can be sufficiently exhibited.

  It is preferable that the composition for cured conductive resin of the present invention further contains a filler, resin beads, or the like as long as the conductivity of the obtained cured cured resin is not impaired. In addition, various additives such as a colorant, a curing agent, a crosslinking agent, an ultraviolet shielding agent, an ultraviolet absorber, and a surface conditioner (leveling agent) are added to the composition for cured conductive resin of the present invention as necessary. May be included.

  Examples of the filler include inorganic fine particles or organic fine particles. When inorganic fine particles are contained as a filler in the composition for a cured conductive resin, the strength of the resulting cured conductive resin is improved, and the organic fine particles are used as a filler in the composition for a cured cured resin. When is contained, the elasticity of the obtained conductive resin cured product is improved. For example, when inorganic fine particles are included as a filler, a cured conductive resin that is preferably used as a hard coat layer having conductivity can be obtained.

  The inorganic fine particles are formed of an inorganic compound such as a metal or an oxide thereof, a nitride thereof, a sulfide thereof or a halide thereof. The inorganic compound forming the inorganic fine particles may contain two or more kinds of metals. Examples of such inorganic fine particles include silica, alumina, zirconia, titania, zirconia, ceria, zinc oxide, indium tin oxide (ITO), antimony tin oxide (ATO), zinc tin oxide (AZO), fluorine-doped indium tin oxide ( FTO), fine particles such as gold, silver, platinum and copper are used. Among these, from the viewpoint of adjusting the refractive index of the resulting cured cured resin, it is preferable to use fine particles of titania, zirconia, ceria, zinc oxide, and the conductivity of the obtained cured cured resin. From the viewpoint of improving the above, it is preferable to use conductive fine particles of tin oxide, tin-doped indium oxide, tin-doped antimony oxide, antimony oxide, tin-doped zinc oxide, gold, silver, platinum, or copper.

These inorganic fine particles are also preferably used when it is necessary to adjust the refractive index of the cured conductive resin. In order to reduce the refractive index, inorganic fine particles having a refractive index of 1.55 or less are preferably used. Examples of such inorganic fine particles include alumina Al ₂ O ₃ (refractive index 1.53), silica SiO ₂ (refractive index 1.46), magnesium fluoride MgF ₂ (refractive index 1.38), calcium fluoride CaF _2. (Refractive index 1.36) and the like can be exemplified. Among them, as described above, it is preferable to select and use a colloidally dispersible solvent or monomer and / or oligomer. When a particularly low refractive index is required, it is preferable to use colloidal silica (SiO ₂ ) fine particles among the inorganic fine particles exemplified above. In addition, when priority is given to imparting sufficient hardness to the coating film, it is preferable to use alumina (Al ₂ O ₃ ) fine particles.

  As the inorganic fine particles, inorganic fine particles having an outer shell layer and porous or hollow inside are preferably used. Such inorganic fine particles have a structure in which a gas is filled and / or a porous structure containing a gas. Therefore, when the gas is air having a refractive index of 1.0, the fine particles are contained in the fine particles in comparison with the original refractive index of the fine particles. The refractive index decreases in proportion to the air occupation ratio. Specific examples of such inorganic fine particles include aggregates of porous silica fine particles in the product name Nipsil and Nipgel manufactured by Nippon Silica Kogyo Co., Ltd., which are commercially available products, and manufactured by Nissan Chemical Industries, Ltd. Colloidal silica UP series (trade name) having a structure connected in a shape, and hollow colloidal silica manufactured by Catalyst Kasei Kogyo Co., Ltd. can be exemplified, and among them, those within the preferred particle diameter range of the present invention Can be used.

  In order to improve the refractive index, the refractive index can be adjusted with inorganic fine particles in the range of 1.46 to 2.00. The particle diameter of the inorganic fine particles used is preferably 100 nm or less. Specific examples of such inorganic fine particles (in parentheses indicate refractive index) include zinc oxide (1.90), titania (2.3 to 2.7), ceria (1.95), tin-doped indium oxide ( 1.95), antimony-doped tin oxide (1.80), yttria (1.87), zirconia (2.0) and the like.

  Organic fine particles include polyolefins, fluoropolymers, polysulfones, polyesters, polyvinyl acetals, polyvinyl alcohols, polyamides, polyimides, polyurethanes, polyacryls, polystyrenes, polyketones, silicones, poly Fine particles composed of a polymer such as lactic acid or cellulose, or a copolymer thereof. From the viewpoint of improving the conductivity of the cured conductive resin, the organic fine particles are preferably coated with a conductive inorganic coating film or the above-described conductive inorganic fine particles having a particle diameter smaller than that of the organic fine particles.

  As the filler, it is preferable to use conductive fine particles from the viewpoint of improving the conductivity of the cured conductive resin. As the conductive fine particles, the above-described tin oxide, antimony oxide, ITO, ATO, AZO, FTO, gold, silver, platinum, copper conductive inorganic fine particles, or surface treatment for imparting conductivity was performed. Organic fine particles are mentioned. Examples of the surface treatment for imparting conductivity include a treatment for coating tin oxide, antimony oxide, ITO, ATO, AZO, FTO, etc. on the above-mentioned organic fine particles, and a hydrophilic group of the above-mentioned hydrophilic group-containing compound. For example, a treatment of adsorbing or binding a functional group that contributes to conductivity, such as a hydrophilic group, to the organic fine particles described above.

  Further, as the filler, it is preferable to use fine particles having a polymerizable functional group on the surface from the viewpoint of improving the strength of the cured conductive resin. Examples of such fine particles include inorganic fine particles or organic fine particles in which a coupling agent, a low molecular weight organic compound or a polymer is adsorbed or bonded to the surface, or organic fine particles produced using a monomer having a polymerizable functional group, etc. Is mentioned. When inorganic fine particles are used as the filler, it is preferable to perform surface treatment such as plasma discharge treatment or corona discharge treatment from the viewpoint of improving compatibility with the binder resin.

  When transparency is required for the cured conductive resin, the average particle size of the fine particles used for the filler is preferably 5 to 300 nm. The blending ratio of the filler is preferably 0.1 to 300% by weight, particularly preferably 0.3 to 200% by weight, based on the solid content of the binder resin or the like.

  When the obtained cured resin resin is transparent, the resin beads are preferably contained in the composition for cured resin resin as long as the conductivity of the cured resin resin is not impaired. When the resin bead is contained in the composition for cured conductive resin, the resulting cured conductive resin is less likely to reflect incident light. Therefore, for example, a conductive layer preferably used as an antiglare layer having conductivity. Can be obtained.

  The filler used as the antiglare layer may be spherical, for example, a spherical or elliptical bead, and preferably a spherical bead. The filler may be an inorganic bead or an organic bead as long as it exhibits antiglare properties, but a transparent one is preferable. Specific examples of the filler include silica beads as inorganic beads, and resin beads as organic beads. The filler preferably has a refractive index in the range of 1.40 to 1.60. The reason is that the refractive index of the cured conductive resin usually shows a value of 1.45 to 1.55, so that the refractive index of the filler approximates the refractive index of the ionizing radiation curable resin. This is because it is possible to impart antiglare properties while maintaining the transparency of the cured conductive resin.

  Examples of resin beads having a refractive index within such a range (1.40 to 1.60) include silica beads (refractive index: 1.46) and polymethyl methacrylate beads (refractive index: 1.49). Polycarbonate beads (refractive index: 1.58), polystyrene beads (refractive index: 1.50), polyacryl styrene beads (refractive index: 1.57), polyvinyl chloride beads (refractive index: 1.54), etc. Can be mentioned.

  The particle size of the resin beads is preferably 3 to 8 μm. The blending ratio of the resin beads is usually 2 to 30 parts by weight and preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the binder resin.

  The composition for cured conductive resin preferably contains an anti-settling agent together with the resin beads. When such an anti-settling agent is contained in the composition together with the resin beads, the resin beads are difficult to settle in the composition for a cured conductive resin, and a coating film or a molded body is formed in the molding process. It becomes easy. On the other hand, when the precipitant is not included in the conductive resin cured product-soluble composition, the resin beads are uniformly dispersed in the molding process because the resin beads are precipitated in the conductive resin cured composition. Thus, it is necessary to form a coating film or a molded body while stirring.

  As an anti-settling agent, silica beads having a particle size of 0.5 μm or less, preferably 0.1 to 0.25 μm can be used. The blending ratio of the anti-settling agent is preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the binder resin. When the blending ratio of the anti-settling agent exceeds 0.1 parts by weight, the transparency of the conductive resin cured product decreases, and when the blending ratio of the anti-settling agent is less than 0.01 parts by weight. The sedimentation of the resin beads cannot be prevented.

  In addition, when using electroconductive resin hardened | cured material as an anti-glare layer, it is preferable that the film thickness at the time of hardening exists in the range of 0.1-100 micrometers, Preferably it is 0.8-20 micrometers. When the film thickness at the time of curing is within this range, the function as an antiglare layer can be sufficiently exhibited.

  The preferred shape of the antiglare layer is that the average particle size of the fine particles is R (μm), the ten-point average roughness of the unevenness of the antiglare layer is Rz (μm), and the average interval of the unevenness of the antiglare layer is Sm (μm). ), And when the average inclination angle of the concavo-convex part is θa, 30 ≦ Sm ≦ 200, 0.90 ≦ Rz ≦ 1.60, 1.3 ≦ θa ≦ 2.5, 0.3 ≦ R ≦ 10, Those satisfying the above are preferred. The ten-point average roughness Rz conformed to JIS B 0601-1994.

  Further, as another preferred embodiment of the antiglare layer, Δn = | n1-n2 | <0.1 is satisfied when the refractive indexes of the fine particles and the cured conductive resin are n1 and n2, respectively. An antiglare layer having a haze value of 55% or less inside the antiglare layer is preferable.

  When the conductive resin cured composition used as a hard coat layer or an antiglare layer is applied to the surface of the display as described above, the refractive index is increased on the surface in order to improve the visibility. A low refractive index layer having a refractive index in the range of 1.20 to 1.45 is formed as an antireflection layer, or a high refractive index layer having a refractive index in the range of 1.46 to 2.00 and the above low refractive index layer. The laminate can also be formed as an antireflection layer.

  When a hard coat layer or an antiglare layer is separately provided on the surface of the display, the display substrate and the hard coat are made so that the cured resin is in a range of 0.1 to 5 μm after curing. It can also be formed between the layers and the antiglare layer and / or on the hard coat layer and the antiglare layer. When a layer made of a cured conductive resin is formed on a hard coat layer or an antiglare layer, the refractive index of the cured antistatic resin can be adjusted in the range of 1.20 to 1.45 with inorganic fine particles. When the refractive index of the antistatic resin cured product is adjusted in the range of 1.46 to 2.00, it can be used as a high refractive index layer having an antireflection function. .

(Formation process)
A formation process is a process of forming a coating film or a molded object with the composition for conductive resin hardened | cured materials prepared at the preparation process. The coating film is formed by coating or printing the composition for a cured conductive resin on a desired substrate. Moreover, formation of a molded object is performed by shape | molding the composition for conductive resin hardened | cured materials in a desired shape. Here, the coating film formed of the composition for cured conductive resin becomes a conductive resin cured film, and the molded body formed of the composition for cured conductive resin becomes a conductive resin cured molded body.

  As a base material, a material and a shape are not specifically limited, Molded objects, such as a sheet form which consists of glass or a plastic, or plate shape, can be mentioned. Examples of the plastic include triacetate cellulose (TAC), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, acrylic resin; polyurethane resin; polyester; polycarbonate; polysulfone; polyether; trimethylpentene; Ether ketone; (meth) acrylonitrile and the like. Specific examples of the base material include various optical films that need to be provided with antistatic performance such as an antireflection sheet and an antiglare sheet, and film base materials such as a film substrate for LCD and an organic EL film base material. Can do. When the substrate is an optical sheet, the thickness is usually about 25 μm to 1000 μm.

  Examples of the coating method include spin coating, dip coating, spray coating, slide coating, bar coating, roll coating, meniscus coating, and bead coater. In addition, examples of the printing method include a flexographic printing method and a screen printing method. When the printing method is used, a coating film having a predetermined pattern can be formed. In addition, it is preferable that the coating film of the composition for conductive resin cured | curing material is provided in the surface on the opposite side to the functional surface so that the optical characteristic of an optical sheet may not be prevented by the conductive resin cured film.

  The thickness of the coating film varies depending on the function or the like when the substrate on which the coating film is formed or the obtained conductive resin cured film is used as a functional film. For example, when the conductive resin cured film is used as a hard coat layer, the thickness of the coating film is a thickness after curing, and is usually 0.1 to 100 μm, preferably 0.8 to 20 μm. When the thickness of the coating film is less than 0.1 μm after curing, sufficient hard coat performance cannot be obtained, and when the thickness of the coating film exceeds 100 μm after curing In this case, the hard coat layer is easily broken by an impact from the outside.

  The molding method of the composition for a cured conductive resin is appropriately selected according to the shape of the molded body, for example, extrusion molding, pipe molding technology, film / sheet molding method (inflation film molding method, T-die film molding method). ), Stretched film molding method (tenter method, roll method, tubular simultaneous biaxial stretching method), extrusion composite molding (composite film / sheet molding method), blow molding (extrusion blow, accumulator blow molding method, injection blow molding) Method, multilayer blow molding method, injection molding method, etc. The shape of the molded body is appropriately determined according to the intended use of the obtained conductive resin cured molded body, for example, a sheet shape, a plate shape, a disk shape, a cylinder Shape, spherical shape and the like.

(Drying process)
A drying process is a process of drying the organic solvent contained in the coating film or molded object formed in the formation process, and is performed by heating the formed coating film or molded object. In the drying step, the lipophilic group may be dissociated from the hydrophilic group of the hydrophilic group-containing polymer compound contained in the coating film, etc. by heating the coating film, etc., and hydrophilic when the lipophilic group is dissociated. The group is exposed and the conductivity of the resulting cured conductive resin is manifested.

  Although the heating conditions in a drying process differ according to the kind of organic solvent used, heating temperature is 40-200 degreeC normally, and heating time is 10 second-120 minutes.

(Curing process)
A hardening process is a process of hardening the coating film or molded object of the composition for conductive resin hardened | cured materials formed as mentioned above. That is, the curing step when a thermosetting resin is used as the binder resin of the conductive resin cured product composition is a step of heating the coating film or the molded body, and the conductive resin cured product composition The curing step when an ionizing radiation curable resin is used as the binder resin is a step of irradiating the coating film or the molded body with ionizing radiation. In addition, after a hardening process, you may perform an aging process at the temperature of 60 degreeC or more to the coating film or molded object of the composition for conductive resin hardened | cured materials from a viewpoint of accelerating hardening reaction.

  In the curing step, the coating film or the molded body is cured to become a conductive resin cured product. Moreover, the lipophilic group couple | bonded with the hydrophilic group of the hydrophilic group containing polymer compound contained in a coating film or a molded object dissociates by the heating in a hardening process, or irradiation of ionizing radiation. For example, when the lipophilic group is bonded to the hydrophilic group by an ester bond, the ester bond is cleaved by heating or the like, and the lipophilic group is dissociated. As a result, the obtained conductive resin cured product exhibits conductivity because the hydrophilic group of the hydrophilic group-containing polymer compound is exposed. In addition, although the lipophilic group which couple | bonded with the hydrophilic group may not dissociate also by the heating in the above-mentioned drying process and the curing process, the hydrophilic group-containing high content contained in the composition for a cured conductive resin is not sufficient. When a lipophilic group is bonded to a part of the hydrophilic group of the molecular compound, the obtained conductive resin cured product may develop conductivity as described in the adjustment step.

The heating conditions for curing the thermosetting resin that is the binder resin vary depending on the type of the thermosetting resin used, but usually the heating temperature is 80 to 200 ° C. and the heating time is 10 seconds to 12 hours. It is. The ultraviolet irradiation conditions for curing the ultraviolet curable resin as the binder resin vary depending on the type of the ultraviolet curable resin used, but the wavelength is 100 to 350 nm and the irradiation energy (integrated light amount) is 50 to 1000 mJ. / Cm ² . The irradiation condition of the electron beam for curing the electron beam curable resin as the binder resin varies depending on the type of the electron beam curable resin used, but the irradiation energy (integrated energy amount) is 10 to 1000 kV or more. .

  In the curing process, the heating temperature and irradiation energy of ionizing radiation are set higher than the heating temperature actually required for curing, or the heating time and irradiation time of ionizing radiation are actually determined from the heating time necessary for curing, etc. It is preferable to positively dissociate the lipophilic group by setting it to a higher value. By doing in this way, since more hydrophilic groups are exposed, the electroconductivity of the obtained conductive resin cured product is improved.

(Dissociation process)
The dissociation step is an optional step for dissociating the lipophilic group that has not been dissociated from the hydrophilic group of the hydrophilic group-containing polymer compound in the curing step, and the conductivity of the cured conductive resin obtained in this step Is further improved. The dissociation step is performed by heating the cured conductive resin or irradiating the cured cured resin with ionizing radiation after the curing step. The dissociation process may be performed continuously with the curing process, and in this case, it is difficult to clearly distinguish the curing process and the dissociation process.

The heating conditions for dissociating the lipophilic group from the hydrophilic group vary depending on the type of bond between the hydrophilic group and the lipophilic group, but usually the heating temperature is 80 to 200 ° C. and the heating time is 60 to 120 minutes. is there. The ultraviolet irradiation conditions for dissociating the lipophilic group from the hydrophilic group are a wavelength of 100 to 350 nm and an irradiation energy (integrated light amount) of 80 to 250 mJ / cm ² . As for the irradiation condition of the electron beam for dissociating the lipophilic group from the hydrophilic group, the irradiation energy (integrated energy amount) is 80 to 500 kV.

  In addition, the dissociation step may be performed by placing the conductive resin cured product in an acidic or basic atmosphere. Specifically, the parent resin can be obtained by immersing the cured conductive resin in an acidic solution or a basic solution, or by using a photoacid generator or a photobase generator that generates an acid or a base by the action of light or heat. Oily groups can be dissociated. Such an approach has the advantage that almost all lipophilic groups can be dissociated at room temperature.

(2) Method for producing a cured conductive resin according to the second embodiment:
The method for producing a cured conductive resin according to the second embodiment of the present invention includes a preparation step for preparing a composition for cured conductive resin according to the second embodiment of the present invention, and a composition for cured conductive resin. It is characterized by including the formation process which forms the coating film or molded object of a thing, and the hardening process which hardens a coating film or a molded object. The method for producing a cured conductive resin according to the second embodiment of the present invention may further include a dissociation step after the curing step. Hereinafter, the adjustment process included in the manufacturing method of the cured conductive resin according to the second embodiment will be described. In addition, since the formation process, the curing process, and the dissociation process included in the manufacturing method of the cured conductive resin according to the second embodiment are the same as the manufacturing method of the cured conductive resin according to the first embodiment, The description here is omitted.

  The preparation step in the method for producing a cured conductive resin according to the second embodiment of the present invention is a step of preparing the composition for cured conductive resin according to the second embodiment of the present invention, that is, a plurality of hydrophilic properties. A hydrophilic group-containing polymer compound having a group and at least one resin (hereinafter sometimes referred to as a binder resin) of an ionizing radiation curable resin and a thermosetting resin, This is a step of preparing a solvent-free composition for a cured cured resin, in which at least a part of the lipophilic group is bonded.

  The hydrophilic group-containing polymer compound contained in the composition for cured conductive resin of the present invention has a plurality of hydrophilic groups, and a lipophilic group is bonded to at least a part of the plurality of hydrophilic groups. Therefore, the compatibility with the solventless binder resin is improved. Therefore, a solvent-free composition for a cured cured resin resin can be prepared, and water is not used in the composition for a cured cured resin resin, so that the obtained cured cured resin resin hardly contains moisture. As a result, since moisture hardly oozes out on the surface of the cured conductive resin, the adhesion with the adjacent base material or layer is improved. In addition, since it is difficult for moisture to ooze out on the surface of the conductive cured product, the performance of the element is unlikely to deteriorate even when used in an apparatus including an element that dislikes water.

  As the hydrophilic group-containing polymer compound and the lipophilic group bonded to the hydrophilic group, those similar to the above-described composition for a cured cured resin resin according to the first embodiment are used. Further, a method for bonding a lipophilic group to a hydrophilic group, a preferable polymerization ratio of a monomer having a hydrophilic group in the hydrophilic group-containing polymer compound, and an upper limit and a lower limit of the weight average molecular weight of the hydrophilic group-containing polymer compound Is the same as the above-described composition for cured conductive resin according to the first embodiment.

  The lipophilic group does not need to be bonded to all the hydrophilic groups of the hydrophilic group-containing polymer compound, and only needs to be bonded to such an extent that the hydrophilic group-containing polymer compound is compatible with the binder resin. Good. The specific binding amount of the lipophilic group is appropriately determined according to the binder resin used. In the case where the lipophilic group is bonded only to a part of the hydrophilic group of the hydrophilic group-containing polymer compound, similarly to the above-described composition for a cured conductive resin according to the first embodiment. Even if the lipophilic group does not dissociate in the drying step and the curing step, the obtained conductive resin cured product may exhibit conductivity.

  As the binder resin, the same ionizing radiation curable resin or thermosetting resin as the conductive resin cured product composition according to the first embodiment described above can be used. For the conductive resin cured composition, It is included as a liquid monomer or prepolymer. In addition, as for the composition for conductive resin hardened | cured materials which concerns on a 2nd form, a viscosity is adjusted with the quantity of the monomer contained.

  As the binder resin, when the obtained conductive resin cured product is used as a functional film or a plastic molded body, a resin corresponding to the function required for the functional film or the like is appropriately selected. In particular, since the composition for cured conductive resin according to the second embodiment of the present invention is a solventless type, a variety of resins used without solvent can be selected as the binder resin.

  The composition for cured conductive resin according to the second aspect of the present invention includes a π-conjugated polymer compound, a filler, or resin beads, similarly to the composition for cured conductive resin according to the first aspect. Is preferably further included. Moreover, additives, such as a coloring agent and a viscosity modifier, may be contained in this composition for conductive resin cured | curing material as needed.

  As the π-conjugated polymer compound, the same composition as that for the cured conductive resin according to the first embodiment described above is used, and the obtained effect is also described in the column of the manufacturing method according to the first embodiment. This is the same as described in. Further, a preferred combination of a π-conjugated polymer compound and a hydrophilic group-containing polymer compound constituting the electron conductive material, upper and lower limits of the weight average molecular weight of the π-conjugated polymer compound, π in the electron conductive material The preferable blending ratio of the hydrophilic group-containing polymer compound to the conjugated polymer compound is also the same as that described in the column of the production method according to the first embodiment. Furthermore, the blending ratio of the hydrophilic group-containing polymer compound to the binder resin, the blending ratio of the hydrophilic group-containing polymer compound to the π-conjugated polymer compound in the electron conductive material, and the blending ratio of the electron conductive material to the binder resin Is the same as the above-described composition for cured conductive resin according to the first embodiment.

  As the filler and resin beads, the same material as the composition for cured conductive resin according to the first embodiment described above is used, and the obtained effect is also described in the column of the manufacturing method according to the first embodiment described above. It is the same as described. Further, the blending ratio of the filler and the resin beads is the same as in the case of the conductive resin cured product composition according to the first embodiment.

[Hardened conductive resin]
As described above, since the cured conductive resin obtained by the production method of the present invention is produced by the composition for cured conductive resin that does not use water as a solvent, it hardly contains moisture. As a result, the cured conductive resin is less likely to seep out of water from the surface, so that the adhesion with the adjacent substrate or layer is improved, and the device includes elements that dislike water. Are preferably used. Here, the cured conductive resin does not contain water at all, or it is a trace amount that does not deteriorate the adhesion to the substrate adjacent to the cured conductive resin or the performance of the element that dislikes water. Fresh water may be included. In addition, since the cured conductive resin of the present invention is obtained by the production method as described above, a lipophilic group may be bonded to a part of the hydrophilic group of the hydrophilic group-containing polymer compound.

  The cured conductive resin obtained by the production method of the present invention includes a hydrophilic group-containing polymer compound having a plurality of hydrophilic groups and an organic solvent-soluble or solventless binder resin, and the hydrophilic groups The contained polymer compound is dispersed in the binder resin. That is, in the cured conductive resin obtained by the production method of the present invention, the hydrophilic group-containing polymer compound is dispersed without being aggregated in the binder resin that is not water-soluble.

  The conductive resin cured product obtained by the production method of the present invention has an effect of high transparency because the hydrophilic group-containing polymer compound having a hydrophilic group is dispersed in the binder resin. Specifically, this conductive resin cured product can ensure transparency of 50% or more in terms of light transmittance. When the conductive resin cured product is used for an application such as an optical sheet or a functional film formed on the optical sheet, the light transmittance is preferably 80% or more.

  Moreover, the conductive resin cured product obtained by the production method of the present invention has an effect of high strength because the hydrophilic group-containing polymer compound having a hydrophilic group is dispersed in the binder resin. Specifically, this conductive resin cured product can ensure strength of H to 6H in pencil hardness. Here, the pencil hardness is measured by “scratch hardness (pencil method)” defined in JIS K5600-5-4: 1999.

  Furthermore, since the hydrophilic group-containing polymer compound having a hydrophilic group is dispersed in the binder resin, the conductive resin cured product obtained by the production method of the present invention is electrically conductive inside the conductive resin cured product. Has the effect of being uniform and difficult to change.

  The conductive resin cured product obtained by the production method of the present invention is used as a conductive resin cured film or a conductive resin cured molded body used for applications such as antistatic and electromagnetic wave shielding.

  The conductive resin cured film is provided on an optical sheet such as an antireflection sheet or an antiglare sheet, and is used as an antistatic film or an electromagnetic wave shielding film. Further, it is also used as an antistatic film or an electromagnetic wave shielding film having other functions such as hard coat property, antiglare property or antireflection property.

  In addition, as the conductive resin cured molded body, various optical sheets having antistatic properties and electromagnetic wave shielding properties (for example, antireflection sheets, antiglare sheets, light scattering sheets, lens sheets, heat ray reflecting sheets, ultraviolet ray reflecting sheets, heat rays, etc.) Absorption sheet, ultraviolet absorption sheet, polarizing film, polarizer film, high viewing angle film, retardation film, optical compensation film, brightness enhancement film, light guide plate, prism sheet, LCD film substrate, organic EL film substrate, OHP film , Phosphorescent film, hologram, etc.).

When the conductive resin cured product obtained by the production method of the present invention is used for antistatic applications, the conductivity is preferably 10 ¹³ Ω / cm ² or less in terms of surface resistance. Moreover, when the conductive resin cured product of the present invention is used for electromagnetic wave shielding, the conductivity is preferably 10 ⁸ Ω / cm ² or less in terms of surface resistance. The conductivity of the cured conductive resin is determined depending on the type of the hydrophilic group-containing polymer compound used, the blending amount of the hydrophilic group-containing polymer compound, the exposure amount of the hydrophilic group possessed by the hydrophilic group-containing polymer compound, or It is appropriately adjusted by adding a π-conjugated polymer compound.

  When the conductive resin cured product obtained by the production method of the present invention is used as a hard coat layer, it preferably has scratch resistance that is difficult to be damaged when a display device is produced or used. Specifically, the scratch resistance of the cured conductive resin is preferably such that the minimum load at which a change in haze value is observed is 100 g or more in the following scratch resistance test. In this abrasion resistance test, the surface of the cured conductive resin was rubbed 10 times with # 0000 steel wool, and a change of 1% or more was observed between the haze value measured thereafter and the haze value before friction. This is a test for evaluating the scratch resistance according to the size of the minimum load when it is recognized. The larger the minimum load, the better the scratch resistance.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples. In Examples 1 to 16 and Comparative Examples 1 and 2, conductive resin cured films having hard coat properties were produced as the cured conductive resin.

Example 1
Using polystyrene sulfonic acid (manufactured by Aldrich; product number: 56,122-3; 18 wt% aqueous dispersion), using an ultracentrifuge (manufactured by Beckman Coulter, model number: OptimaXL-100K) at 20 ° C. The solid content was separated under the condition of 90,000 rpm for 5 hours. Next, the solid content was filtered off with a filter, and the obtained solid content was dried at 150 ° C. for 1 hour and then pulverized with an agate mortar. Thereafter, the pulverized solid content was dried under reduced pressure at 150 ° C. for 12 hours to obtain a powdery hydrophilic group-containing polymer material.

  Next, a mixture of 100 parts by weight of the above powdery hydrophilic group-containing material and 50 parts by weight of phosphorus pentachloride was boiled at 170 ° C. for 10 hours, and then distilled. The obtained distillate was added to tetrahydrofuran and filtered, and 200 parts by weight of ethanol and 60 parts by weight of pyridine were added to the filtrate, and the mixture was refluxed with stirring for 24 hours for esterification. Thereafter, the obtained reaction mixture was filtered, and the solvent was distilled off from the filtrate to obtain 80 parts by weight of a powdery organic polymer material. About this organic polymer material, the solubility with respect to 100 mass times organic solvent (toluene, methyl ethyl ketone, isopropyl alcohol) was investigated. As a result, the organic polymer material was well dissolved in any organic solvent. Further, the electron conductive material before the esterification reaction was examined for solubility in an organic solvent in the same manner, and it was not soluble in any organic solvent.

  1.0 part by weight of a hydrophilic group-containing polymer compound soluble in an organic solvent obtained as described above, 9.0 parts by weight of pentaerythritol triacrylate (PETA) as a binder resin, and a photopolymerization initiator As a result, 0.4 part by weight of Irgacure 184 (trade name) manufactured by Ciba Specialty Chemicals was diluted with 90 parts by weight of an organic solvent methyl ethyl ketone to prepare a composition for a cured cured resin.

  A sheet made of triacetate cellulose (TAC) is used as a base material, and the above-mentioned composition for a cured conductive resin is applied to the base material by a bar coating method to form a coating film, which is heated at 40 ° C. for 1 minute. As a result, the organic solvent was removed by drying.

Next, the coating film was cured by irradiating with ultraviolet rays at an irradiation dose of 200 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., Ltd., light source: H bulb). Resin cured film (thickness: 3 μm) was obtained.

(Example 2)
1.0 part by weight of a hydrophilic group-containing polymer compound soluble in an organic solvent obtained in the production of the cured conductive resin film of Example 1, and Composeran E102 (product of Arakawa Chemical Industries, Ltd.) as a binder resin Name, solid content: 48.6 wt%) 18.5 parts by weight were diluted with 80.5 parts by weight of the organic solvent methyl ethyl ketone to prepare a composition for a cured conductive resin.

  A sheet made of triacetate cellulose (TAC) is used as a base material, and the above-mentioned composition for a cured conductive resin is applied to the base material by a bar coating method to form a coating film, which is heated at 40 ° C. for 1 minute. As a result, the organic solvent was removed by drying.

  Next, the coating film was cured by heating at 120 ° C. for 1 hour to obtain a conductive resin cured film (thickness: 3 μm) of Example 2.

(Example 3)
As a mixture of a hydrophilic group-containing polymer compound having a hydrophilic group and a π-conjugated polymer compound (π-conjugated conductive material), polystyrene sulfonate and poly (2,3-dihydrothieno [3,4-b]- Using an aqueous dispersion with 1,4-dioxin (manufactured by Sigma Aldrich, product number: 48,309-5), a lipophilic group was bonded to the hydrophilic group by an esterification reaction.

  First, the above-mentioned aqueous dispersion was separated into solids using an ultracentrifuge (Beckman Coulter, model number: OptimaXL-100K) under the conditions of 20 ° C., 90,000 rpm, and 5 hours. . Next, the solid content was filtered off with a filter, and the obtained solid content was dried at 150 ° C. for 1 hour and then pulverized with an agate mortar. Thereafter, the pulverized solid was dried at 150 ° C. for 12 hours under reduced pressure to obtain a powdery electron conductive material.

  Next, a mixture of 100 parts by weight of the above powdered electron conductive material and 38 parts by weight of phosphorus pentachloride was boiled at 170 ° C. for 10 hours and then distilled. The obtained distillate was added to tetrahydrofuran and filtered, and 48 parts by weight of ethanol and 30 parts by weight of pyridine were added to the filtrate, and the mixture was refluxed with stirring for 24 hours for esterification. Thereafter, the obtained reaction mixture was filtered, and the solvent was distilled off from the filtrate to obtain 63 parts by weight of a powdery electron conductive material. About this electron conductive material, the solubility with respect to 100 mass times organic solvent (toluene, methyl ethyl ketone, isopropyl alcohol) was investigated. As a result, this electron conductive material was well dissolved in any organic solvent. Further, the electron conductive material before the esterification reaction was examined for solubility in an organic solvent in the same manner, and it was not soluble in any organic solvent.

  1.0 parts by weight of an electron conductive material soluble in an organic solvent obtained as described above, 9.0 parts by weight of pentaerythritol triacrylate (PETA) as a binder resin, and Ciba as a photopolymerization initiator. 0.4 parts by weight of Irgacure 184 (trade name) manufactured by Specialty Chemicals was diluted with 90.0 parts by weight of an organic solvent methyl ethyl ketone to prepare a composition for a cured cured resin.

  A sheet made of triacetate cellulose (TAC) is used as a base material, and the above-mentioned composition for a cured conductive resin is applied to the base material by a bar coating method to form a coating film, which is heated at 40 ° C. for 1 minute. As a result, the organic solvent was removed by drying.

Next, the coating film was cured by irradiating with ultraviolet rays at an irradiation dose of 200 mJ / cm ² using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., Ltd., light source: H bulb). Resin cured film (thickness: 3 μm) was obtained.

Example 4
1.0 part by weight of an electron conductive material soluble in an organic solvent obtained in the production of the cured conductive resin film of Example 3 and COMPOSELAN E102 (trade name, solid, manufactured by Arakawa Chemical Industries, Ltd.) as a binder resin (18.6 parts by weight: 48.6% by weight) was diluted with 90.0 parts by weight of an organic solvent methyl ethyl ketone to prepare a composition for a cured cured resin.

  Using a sheet of polyethylene terephthalate (PET) that has been subjected to easy adhesion treatment as a base material, a coating film is formed on the base material by applying the above-mentioned composition for a cured conductive resin by a bar coating method, The organic solvent was dried and removed by heating at 40 ° C. for 1 minute.

  Next, the coating film was cured by heating at 120 ° C. for 1 hour to obtain a cured conductive resin film (thickness: 3 μm) of Example 4.

(Example 5)
In the production of the cured conductive resin film of Example 3, colloidal silica as a filler (manufactured by Nissan Chemical Industries, Ltd. Name: MEK-ST, average particle size: 15 nm, solid content 20% by weight) The conductive resin cured film of Example 5 (thickness: 3 μm) is the same as Example 3 except that 50 parts by weight is contained. )

(Example 6)
In preparation of the cured conductive resin film of Example 4, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-) with respect to 210 parts by weight of the binder resin when preparing the composition for cured conductive resin. A cured conductive resin film (thickness: 3 μm) of Example 6 was obtained in the same manner as Example 4 except that 50 parts by weight of ST, average particle diameter: 15 nm, solid content 20% by weight) was contained. .

(Example 7)
In the preparation of the cured conductive resin film of Example 3, when preparing the composition for a cured conductive resin, 10 parts by weight of a methyl ethyl ketone dispersion of antimony-doped tin oxide fine particles surface-treated with respect to 10 parts by weight of the binder resin. A conductive resin cured film (thickness: 3 μm) of Example 7 was obtained in the same manner as in Example 3 except that the content was by weight.

  The surface-treated antimony-doped tin oxide fine particle-methyl ethyl ketone dispersion is composed of 20 parts by weight of tin oxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., trade name SN-100P, primary particle size 20 nm, solid content 20% by weight). Was dispersed in 80 parts by weight of methyl ethyl ketone, and 5 parts by weight of 3-methacryloxypropylmethyldimethoxysilane was added, followed by heating at 50 ° C. for 1 hour. The surface-treated tin oxide fine particles have a methacryloxy group, which is a polymerizable group, added to the surface.

(Example 8)
1.0 part by weight of a hydrophilic group-containing polymer compound soluble in an organic solvent obtained in the preparation of the cured conductive resin film of Example 1, and a silsesquioxane OX-SQ having an oxetanyl group as a binder resin ( (Product name: Toagosei Co., Ltd.) 9.0 parts by weight and TPS-103 (trade name: Midori Chemical Co., Ltd.) 0.3 parts by weight as a photopolymerization initiator diluted with 90 parts by weight of organic solvent isopropanol And the composition for conductive resin hardened | cured materials was prepared. The conductive resin cured film was formed on triacetate cellulose (TAC) in the same manner as in Example 1 to obtain a conductive resin cured film (thickness: 3 μm) of Example 8.

Example 9
1.0 part by weight of an electron conductive material soluble in an organic solvent obtained in the production of the cured conductive resin film of Example 3, and silsesquioxane OX-SQ having an oxetanyl group as a binder resin (trade name: 9.0 parts by weight of Toagosei Co., Ltd.) and 0.3 parts by weight of TPS-103 (trade name: Midori Chemical Co., Ltd.) as a photopolymerization initiator were diluted with 90 parts by weight of an organic solvent isopropanol, A composition for cured conductive resin was prepared. Formation of the cured conductive resin film on triacetate cellulose (TAC) was carried out in the same manner as in Example 3 to obtain the cured conductive resin film (thickness: 3 μm) of Example 9.

(Example 10)
5% by weight of 3-methacryloxypropylmethyldimethoxysilane is added to 100% by weight of a methyl ethyl ketone dispersion of colloidal silica (solid content: 20% by weight) used in the filler of Example 5, and heat-treated at 50 ° C. for 1 hour. As a result, a surface-treated hollow silica fine particle 20 wt% methyl ethyl ketone dispersion was obtained. Using this surface-treated colloidal silica, a cured conductive resin film (thickness: 3 μm) of Example 10 was obtained in the same manner as Example 5.

(Example 11)
After 0.5 parts by weight of self-doped polythiophene (trade name: ADS2010P, powdered solid) manufactured by American Dye Source, Inc. was ground in an agate mortar, it was placed in a 100 ml eggplant flask and tetrahydrofuran (THF) 50.0 parts by weight were added and stirred. When 1.5 parts by weight of dibutyl sulfate was added thereto and stirred at room temperature for 5 days, a solution in which THF was colored brown was obtained. Thereafter, the reaction solution was filtered to remove unreacted substances and impurities, and tetrahydrofuran was removed from the solution by a rotary evaporator to obtain a solid. This was washed with hexane to remove the remaining dibutyl sulfate, and after vacuum drying, a butyl esterified organic polymer material was obtained. This organic polymer material was soluble in 100 mass times toluene, and the solid before the butyl esterification treatment was insoluble. Using this, a composition for a cured conductive resin was prepared in the same manner as in Example 3. Formation of the cured conductive resin film on triacetate cellulose (TAC) was carried out in the same manner as in Example 3 to obtain the cured conductive resin film (thickness: 3 μm) of Example 11.

(Example 12)
A conductive resin cured composition and a conductive resin cured film (thickness: 3 μm) of Example 12 were prepared in the same manner as in Example 8 except that the organic polymer material obtained in Example 11 was used. Obtained.

(Example 13)
The composition for cured conductive resin and the cured cured conductive resin film of Example 13 (thickness: 3 μm) were prepared in the same manner as in Example 2 except that the organic polymer material obtained in Example 11 was used. Obtained.

(Example 14)
100.0 parts by weight of the composition for curing a conductive resin obtained in Example 3 was removed by using a rotary evaporator to remove the organic solvent methyl ethyl ketone, and a conductive material comprising 10.0 parts by weight of an electron conductive material and a binder resin. A composition for cured resin was prepared. After coating this composition for a cured conductive resin on a 0.5 mm Teflon (registered trademark) sheet by the bar coating method, the composition is irradiated with ultraviolet rays with an irradiation dose of 500 mJ / cm ² using an ultraviolet irradiation device. Then, the coating film was cured, and then peeled off from the Teflon (registered trademark) sheet, to obtain a conductive resin cured film of Example 14 (thickness: 100 μm, No. 14-1). A film (thickness: 100 μm, No. 14-2) irradiated with ultraviolet rays of 500 mJ / cm ² for the purpose of increasing the hydrophilic group amount of the electron conductive material contained in the obtained conductive resin cured film; A film (thickness: 100 μm, No. 14-3) immersed in a 1N aqueous sodium hydroxide solution at 40 ° C. for 30 seconds was also produced.

(Example 15)
A polyethylene terephthalate (PET) film (thickness: 100 μm) was prepared, and the conductive resin curing composition obtained in Example 3 was applied to the surface by a bar coating method. Then, after removing the solvent by drying, using an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb), ultraviolet irradiation was performed at an irradiation dose of 108 mJ / m ² , and curing was performed. Resin cured film (thickness: 5 μm) was obtained.

Next, a low refractive index layer composition blended at the following ratio was applied to the surface of the cured conductive resin film by the bar coating method, and after removing the solvent by drying, an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd.) By using a company, a light source H bulb), an ultraviolet ray was irradiated at an irradiation dose of 192 mJ / m ² and cured to obtain an optical laminate. The film thickness was adjusted so that the minimum value of the reflectance was around 550 nm.

  Composition for low refractive index layer: Fluorine atom-containing binder resin (trade name: Optool AR100, manufactured by Daikin Industries) 13 parts by weight / colloidal silica (trade name: MEK-ST, manufactured by Nissan Chemical Industries) 5 parts by weight / photocuring Resin: PET30 (trade name: manufactured by Nippon Kayaku Co., Ltd.) 2 parts by weight / photopolymerization initiator: Irgacure 907 (trade name: manufactured by Ciba Specialty Chemicals) 0.3 part by weight / methyl isobutyl ketone 85.3 parts by weight

  Measurement of reflectance: The absolute reflectance of the outermost surface of the film was measured using a spectrophotometer (UV-3100PC: trade name) manufactured by Shimadzu Corporation.

(Example 16)
The composition for hard coats blended in the following proportions on the conductive resin cured films (No. 14-1, No. 14-2, No. 14-3) obtained in Example 14 by the bar coat method. Coated. Then, after removing the solvent by drying, using an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., light source H bulb), ultraviolet irradiation was performed at an irradiation dose of 108 mJ / m ² , and curing was performed. Resin cured films (thickness: 5 μm, No. 16-1, No. 16-2, No. 16-3) were obtained.

Next, the same low refractive index layer composition as in Example 15 was applied to the surface of the cured conductive resin film by the bar coating method, and after removing the solvent by drying, an ultraviolet irradiation device (Fusion UV System Japan) Using a light source H bulb, Inc., an ultraviolet ray was irradiated at an irradiation dose of 192 mJ / m ² and cured to obtain an optical laminate. The film thickness was adjusted so that the minimum value of the reflectance was around 550 nm.

  Hard coat composition; photocurable resin: PET30 (trade name: manufactured by Nippon Kayaku Co., Ltd.) 100 parts by weight / photoinitiator: Irgacure 184 (trade name: manufactured by Ciba Specialty Chemicals) 4 parts by weight / 100 parts by weight of isopropyl alcohol Part

(Comparative Example 1)
5.6 parts by weight of polystyrene sulfonic acid (manufactured by Aldrich; product number: 56,122-3; 18% by weight aqueous dispersion)) and 9.0 parts by weight of pentaerythritol acrylate were used with 85.4 parts by weight of water. Thus, a composition for cured conductive resin was prepared, but the binder resin was not dissolved in water, and a uniform solution or dispersion was not obtained.

(Comparative Example 2)
4. In the production of the cured conductive resin film of Example 1, polystyrene sulfonic acid (manufactured by Aldrich; product number: 56,122-3; 18 wt% aqueous dispersion) is used as the composition for cured conductive resin. 6 parts by weight and 30 parts by weight of an ultraviolet curable water-dispersing polymer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK polymer RP116-EH, 30% by weight aqueous dispersion) are dissolved in 64.4 parts by weight of water. A cured conductive resin film (thickness: 3 μm) of Comparative Example 2 was obtained in the same manner as in Example 1 except that the composition for cured cured resin resin was used.

(Evaluation of conductivity)
The conductivity was evaluated by measuring the surface resistance value of the obtained conductive resin cured film. The surface resistance value is determined in accordance with the provisions of JIS K7194 “Resistivity test method using 4-probe method of conductive plastic” after leaving the cured conductive resin film in an environment of 25 ° C. and 30% humidity for 12 hours. Surface resistance measuring device (manufactured by Dia Instruments Co., Ltd., Lorester EP (measuring range 10 ⁻² to 10 ⁶ Ω)) and surface resistance measuring device (manufactured by Dia Instruments Co., Ltd., Hirestar UP (measuring range 10 ⁴ to 10 ¹³⁾ Ω)). The results are shown in Table 1.

(Evaluation of moisture content)
The moisture content of the obtained conductive resin cured film was evaluated as follows. 25 ml of dehydrated methanol (for trace moisture titration) was taken into the dried titration flask, and Karl Fischer reagent (trade name; for SS low moisture sample) was dropped to the end point to make it anhydrous. Next, 1.0 g of the cured conductive resin film cut into a square with a side of 5 mm was quickly transferred to a titration flask and stirred for 15 minutes to completely extract moisture into the solvent. Thereafter, the same Karl Fischer reagent as described above was dropped into the titration flask, and the water content contained from the amount of the reagent up to the point of time when the water became anhydrous was measured using a Karl Fischer measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., model number; MKA- 210), and the water content was calculated from the water content. The results are shown in Table 1. In addition, as the conductive resin cured film used for this evaluation, in the coating process of each Example and Comparative Example, the composition for a cured conductive resin was Teflon (under 25% humidity and room temperature 25 ° C.). The one coated on a (registered trademark) sheet was used.

(Evaluation of adhesion to substrate)
The adhesion between the obtained cured conductive resin film and the substrate was evaluated in accordance with JIS K5600-5-6: 1999 “Adhesiveness (cross-cut method)”. The results are shown in Table 1. In Table 1, what peeled completely from the base material was set to x, what peeled partially was set to (triangle | delta), and what did not peel was set to (circle).

(Evaluation of light transmission)
The light transmittance of the obtained conductive resin cured film was measured using a spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV-3100PC) as a measuring device. The results are shown in Table 1.

(Evaluation of hardness)
The hardness of the obtained conductive resin cured film was measured by “scratch hardness (pencil method)” defined in JIS K5600-5-4: 1999. The results are shown in Table 1.

(Evaluation of scratch resistance)
The surface of the obtained conductive resin cured film was subjected to 10 reciprocal frictions with a predetermined friction load using # 0000 steel wool, and the haze value thereafter was measured. The haze value was measured by changing the friction load every 200 g within a range of 200 to 1000 g. A haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number: NDH2000) was used for the measurement of the haze value. Then, the scratch resistance of the conductive resin cured film was evaluated by examining the minimum load when a change of 1% or more was observed compared with the haze value of the conductive resin cured film before friction. The results are shown in Table 1.

(Evaluation results)
The conductive resin cured films of Examples 1 to 16 had low moisture content and good adhesion, whereas the conductive resin cured film of Comparative Example 2 had high moisture content and poor adhesion. Moreover, the electroconductive resin cured film of Examples 1-16 was a thing with high all of electroconductivity, light transmittance, and hardness.

Claims (11)

The hydrophilic group of the hydrophilic group-containing polymer compound is esterified or etherified to bond the lipophilic group to the hydrophilic group, thereby having a plurality of hydrophilic groups and one of the plurality of hydrophilic groups. Obtaining a hydrophilic group-containing polymer compound having a lipophilic group bonded to a part thereof ;
A preparation step for preparing a composition for a cured cured resin comprising the hydrophilic group-containing polymer, at least one of an ionizing radiation curable resin and a thermosetting resin, and an organic solvent;
A forming step of forming a coating film or a molded body with the composition for cured conductive resin,
A drying step of drying the organic solvent contained in the coating film or the molded body;
A method for producing a cured conductive resin, comprising: a curing step of curing the coating film or the molded body. The hydrophilic group of the hydrophilic group-containing polymer compound is esterified or etherified to bond the lipophilic group to the hydrophilic group, thereby having a plurality of hydrophilic groups and one of the plurality of hydrophilic groups. Obtaining a hydrophilic group-containing polymer compound having a lipophilic group bonded to a part thereof ;
A preparation step of preparing a solvent-free conductive resin cured composition containing the hydrophilic group-containing polymer compound and at least one of an ionizing radiation curable resin and a thermosetting resin;
A forming step of forming a coating film or a molded body with the composition for cured conductive resin,
A method for producing a cured conductive resin, comprising: a curing step of curing the coating film or the molded body.   2. The method according to claim 1, wherein in at least one of the drying step and the curing step, at least a part of the lipophilic group of the hydrophilic group-containing polymer compound is dissociated from the hydrophilic group. The manufacturing method of electroconductive resin hardened | cured material of description.   3. The method for producing a cured conductive resin according to claim 2, wherein in the curing step, at least a part of the lipophilic group of the hydrophilic group-containing polymer compound is dissociated from the hydrophilic group. .   5. The method according to claim 1, further comprising a dissociation step of dissociating at least part of the lipophilic group of the hydrophilic group-containing polymer compound from the hydrophilic group after the curing step. The manufacturing method of the electroconductive resin hardened | cured material of 1 item | term. Claim 1, wherein the conductive resin cured composition is further seen contains a π-conjugated polymer compound, or with the main chain π conjugated bonds of the hydrophilic group-containing polymer compound, wherein the 6. The method for producing a cured conductive resin according to any one of 5 above. The method for producing a cured conductive resin according to claim 6 , wherein the π-conjugated polymer compound is polythiophene or a polythiophene derivative when the π-conjugated polymer compound is further included . Wherein the hydrophilic group is a sulfonic group, method for producing a conductive resin cured product according to claim 1-7, characterized in that at least one member selected from the group consisting of carboxyl group and phosphoric acid group.   The method for producing a cured conductive resin according to claim 1, wherein the composition for cured conductive resin further includes a filler. A hydrophilic group-containing polymer compound having a plurality of hydrophilic groups, at least one of an ionizing radiation curable resin and a thermosetting resin, and an organic solvent, wherein a part of the plurality of hydrophilic groups is an ester Or a lipophilic group bonded to the hydrophilic group and further containing a π-conjugated polymer compound or having a π-conjugated bond in the main chain of the hydrophilic group-containing polymer compound The composition for hardened | cured conductive resin characterized by the above-mentioned. A composition for a cured solvent-free conductive resin comprising a hydrophilic group-containing polymer compound having a plurality of hydrophilic groups and at least one of an ionizing radiation curable resin and a thermosetting resin, A part of the plurality of hydrophilic groups is esterified or etherified, and a lipophilic group is bonded to the hydrophilic group , and a π-conjugated polymer compound is further included, or the hydrophilic group-containing polymer A composition for cured conductive resin, characterized by having a π-conjugated bond in the main chain of the compound .